Estimation of Nanoparticle's Surface Electrostatic Potential in Solution Using Acid-Base Molecular Probes II: Insight from Atomistic Simulations of Micelles.

Exploiting acid-base indicators as molecular probes is one of the most popular methods for determining the surface electrostatic potential Ψ in hydrophilic colloids like micellar surfactant solutions and related systems. Specifically, the indicator's apparent acidity constant index is measured in the colloid solution of interest and, as a rule, in a nonionic surfactant solution; the difference between the two is proportional to Ψ. Despite the widespread use of this approach, a major problem remains unresolved, namely, the dissimilarity of Ψ values obtained with different indicators for the same system.

Estimation of Nanoparticle's Surface Electrostatic Potential in Solution Using Acid-Base Molecular Probes I: Implementation for Surfactant Micelles.

Surface electrostatic potential Ψ is a key characteristic of colloid particles. Since the surface of the particles adsorbs various compounds and facilitates chemical reactions between them, Ψ largely affects the properties of adsorbed reactants and governs the flow of chemical reactions occurring between them. One of the most popular methods for estimating Ψ in hydrophilic colloids, such as micellar surfactant solutions and related systems, is the application of molecular probes, predominantly acid-base indicator dyes.

Unexpected Colloidal Stability of Fullerenes in Dimethyl Sulfoxide and Related Systems.

It is known that fullerenes are poorly soluble in polar solvents, but readily form colloidal solutions in such media. These solutions are typically solvophobic (hydrophobic when prepared in water), that is, thermodynamically unstable colloidal systems with negatively charged particles. To understand the stability factors of a colloidal system, the thresholds for coagulation of a sol or suspension by electrolytes are of key importance.

Formation, Stability, and Coagulation of Fullerene Organosols: C in Acetonitrile-Toluene Solutions and Related Systems.

This paper is aimed at better understanding the nature of C aggregates in organic solvents. As liquid media, acetonitrile-toluene mixed solvents were chosen. At a high content of CHCN, e.

Computing p Shifts Using Traditional Molecular Dynamics: Example of Acid-Base Indicator Dyes in Organized Solutions.

A compound's acidity constant () in a given medium determines its protonation state and, thus, its behavior and physicochemical properties. Therefore, it is among the key characteristics considered during the design of new compounds for the needs of advanced technology, medicine, and biological research, a notable example being pH sensors. The computational prediction of for weak acids and bases in homogeneous solvents is presently rather well developed.

Aminofluoresceins Versus Fluorescein: Peculiarity of Fluorescence.

In this article, we examined the fluorescent properties of 4'- and 5'-aminofluorescein, unsubstituted fluorescein, and its 4'-nitro derivative in a set of solvent systems. Fluorescence lifetimes, quantum yields, time-resolved fluorescence spectra, and quantum chemical calculations allowed clarifying the reasons of the emitting properties in this dye series. In water, the dianions R of aminofluoresceins are practically nonfluorescent; in alcohols, the quantum yields are low.

Aminofluoresceins Versus Fluorescein: Ascertained New Unusual Features of Tautomerism and Dissociation of Hydroxyxanthene Dyes in Solution.

Within the course of this spectroscopic research, we revealed novel features of the protolytic behavior, which extend the knowledge of the chemistry of xanthene dyes and rationalize the utilization of these compounds. In addition to the well-known tautomerism of the molecular form, HR, of fluorescein dyes, new aspects of tautomeric transformation of anions are disclosed. First, for the dyes bearing the substituents in the phthalic acid residue, 4'- and 5'-aminofluoresceins and 4'-fluorescein isothiocyanate, the monoanion HR exists in non-hydrogen-bond donor solvents not only as a tautomer with the ionized carboxylic and nonionized OH group but also as a "phenolate" ion with a nonionized COOH group.

Interaction of Polymethine Dyes with Detonation Nanodiamonds.

Among cationic, anionic, and merocyanine polymethine dyes, the binding to detonation nanodiamond (DND) colloid particles in hydrosol occurs only for negatively charged dye species. This, in view of the positive ζ-potential of the DND used in this study, suggests the predominance of electrostatic interactions over other intermolecular forces in such systems. Indeed, after decorating the merocyanine and the cationic dye by one and two negatively charged sulfopropyl groups, respectively, so that the net charge of their colored species becomes negative, the compounds also demonstrate affinity to the DND particles.

Character of Localization and Microenvironment of Solvatochromic Reichardt's Betaine Dye in Sodium n-Dodecyl Sulfate and Cetyltrimethylammonium Bromide Micelles: Molecular Dynamics Simulation Study.

The problem of using surfactant micellar aqueous solutions as reaction media centers on estimating the polarity of the micellar pseudophase. The most popular approach is the utilization of solvatochromic dyes. Among the last, the strongest ones are the dipolar pyridinium N-phenolate dyes.

Fluorescence of aminofluoresceins as an indicative process allowing one to distinguish between micelles of cationic surfactants and micelle-like aggregates.

Among the vast set of fluorescein derivatives, the double charged R anions of aminofluoresceins are known to exhibit only low quantum yields of fluorescence, [Formula: see text]. The [Formula: see text] value becomes as high as that of the fluorescein dianion when the lone electron pair of the amino group is involved in a covalent bond. According to Munkholm et al (1990 J.

Absorption, fluorescence, and acid-base equilibria of rhodamines in micellar media of sodium dodecyl sulfate.

Rhodamine dyes are widely used as molecular probes in different fields of science. The aim of this paper was to ascertain to what extent the structural peculiarities of the compounds influence their absorption, emission, and acid-base properties under unified conditions. The acid-base dissociation (HR(+)⇄R+H(+)) of a series of rhodamine dyes was studied in sodium n-dodecylsulfate micellar solutions.

Towards better understanding of C60 organosols.

It is of common knowledge that fullerenes form colloids in polar solvents. However, the coagulation via electrolytes and the origin of the negative charge of species are still unexplored. Using a 'radical scavenger' and electrospray ionization spectroscopy (ESI), we proved the formation of ion-radical C60˙(-) and its (probable) transformation into C60(2-) or (C60)2(2-).

Ionization and tautomerism of methyl fluorescein and related dyes.

The protolytic equilibrium of methyl ether of fluorescein is studied in water, aqueous ethanol, and in other solvents. The constants of the two-step dissociation are determined by spectrophotometry. In water, the fractions of the zwitterionic, quinonoid, and lactonic tautomes are correspondingly 11%, 6%, and 83%, as deduced from the UV-visible spectra.

The influence of beta-cyclodextrin on acid-base and tautomeric equilibrium of fluorescein dyes in aqueous solution.

The protolytic equilibrium of fluorescein in aqueous solutions was studied in the presence of cycloheptaamylose (beta-cyclodextrin, or beta-CD). The constants of stepwise ionization of the dye (H(3)R(+)left arrow over right arrowH(2)Rleft arrow over right arrow HR(-)left arrow over right arrowR(2-)), K(a0), K(a1), and K(a2) were determined using vis-spectroscopy at ionic strength 0.05 M (NaCl+buffer) and 25 degrees C.

Medium effects on the prototropic equilibria of fluorescein fluoro derivatives in true and organized solution.

The stepwise ionization (H(3)R(+) <==> H(2)R <==> HR(-) <==> R(2-)) of four fluorescein fluoro derivatives was studied by visible spectroscopy. The pK(a) values were determined in water, in 50 mass % aqueous ethanol, in oil-in-water microemulsions (benzene + CTAB + pentanol-1 in water with 1.0 M KCl; CTAB = cetyltrimethylammonium bromide), and in reversed ones (water + AOT in n-octane; AOT = bis-2-ethylhexylsulphosuccinate or Aerosol OT).

Nature of cationic poly(propylenimine) dendrimers in aqueous solutions as studied using versatile indicator dyes.

Aqueous solutions of four cationic poly(propylenimine) low-generation dendrimers of different architecture and hydrophobicity have been examined as media for acid-base reactions of indicator dyes. The cationic dendrimers in solution can be considered as oligomers of cationic polyelectrolytes, or surfactant-like species, able to form micelles through self-association or sometimes even as unimolecular micelles. The dendrimers influence the ionization constants, tautomeric equilibria, and absorption/emission/excitation spectra of indicator dyes.

2,4,5,7-Tetranitrofluorescein in solutions: novel type of tautomerism in hydroxyxanthene series as detected by various spectral methods.

Stepwise dissociation and tautomerism of 2,4,5,7-tetranitrofluorescein (TNF) were studied by using vis-spectroscopy in dimethylsulfoxide (DMSO), in aqueous acetone, and in cetyl-trimethylammonium chloride (CTAC) micellar solutions at ionic strength of the bulk phase 4.00M KCl. The pK(a) values in DMSO and 90 mass% (CH3)2CO as well as the 'apparent'pK(a)(a) values of the substance in micellar media were determined spectrophotometrically.

Counterion-induced transformations of cationic surfactant micelles studied by using the displacing effect of solvatochromic pyridinium N-phenolate betaine dyes.

In this paper, we demonstrate that the behavior of a set of eight large-sized negatively solvatochromic pyridinium N-phenolate betaine dyes reflects the principle transformations, occurring in aqueous micellar solutions of three cationic surfactants. As surfactants, cetyltrimethylammonium bromide (CTAB), n-octadecyltrimethylammonium chloride (OTAC), and N-cetylpyridinium bromide (CPB) were used. Normally, for such probes coupled with micelles, a red shift of the vis absorption band is expected as a result of a hydrophobization ("drying") of the micellar interface.